Surface treatment agent for substrate, comprising perfluoropolyether group-containing phosphate compound

ABSTRACT

A surface treatment agent for a substrate, comprising a perfluoropolyether group-containing phosphate compound, a coating agent comprising the surface treatment agent and a liquid medium, and a substrate having a surface layer formed from the surface treatment agent or the coating agent.

FIELD OF INVENTION

The present invention relates to a surface treatment agent for asubstrate, comprising a perfluoropolyether group-containing phosphatecompound, and a substrate having a surface layer formed from the surfacetreatment agent.

BACKGROUND OF INVENTION

An article having a substrate, such as an optical article, a display oran optical recording medium, is required to have properties such aswater/oil repellency or stain removability so that water or fouling(such as fingerprints, sebum, sweat, cosmetics, foods, etc.) is lesslikely to attach on the surface, or that fouling, if has attached on thesurface, can easily be removed. For example, if fouling attaches on thesurface of an eyeglass lens, visibility tends to be impaired and visualquality tends to be deteriorated. If fouling attaches on the surface ofan optical recording medium, a trouble is likely to be caused inrecording or reproducing a signal. If fouling attaches on the surface ofa display, the visibility tends to be low, and in the case of a displayprovided with a touch panel, the operation efficiency tends to beadversely affected.

As improvement techniques for an aluminum oxide substrate surface, atechnique for forming a surface layer from a phosphate compound having aperfluoroalkyl group, such as 1H,1H,2H,2H-perfluorodecylphosphonic acid(Non-Patent Document 1), has been known.

PRIOR ART DOCUMENT Non-Patent Document

-   Non-Patent Document 1: J. Phys. Chem. C, 2007, 111, 3956-3962

SUMMARY OF INVENTION Technical Problem

However, according to findings by the present inventor, the surfacelayer described in Non-Patent Document 1 is insufficient in water/oilrepellency, fingerprint stain removability and lubricity. Further, in acase where a substrate having the surface layer as described inNon-Patent Document 1 is repeatedly abraded, the water/oil repellency issubstantially deteriorated due to the abrasion, whereby the abrasionresistance becomes insufficient.

The object of the present invention is to provide a surface treatmentagent capable of imparting excellent water/oil repellency, fingerprintstain removability, abrasion resistance and lubricity to the substratesurface.

Solution to Problem

The present invention provides a surface treatment agent for asubstrate, a coating agent, a substrate having a surface layer and anovel perfluoropolyether group-containing phosphate compound, which havethe following constructions [1] to [14].

[1] A surface treatment agent for a substrate, comprising aperfluoropolyether group-containing phosphate compound.[2] The surface treatment agent according to [1], wherein theperfluoropolyether group-containing phosphate compound is a compoundrepresented by the following formula (1):

B¹—(C_(m)F_(2m)O)_(n1)-A¹  (1)

wherein A¹ is a monovalent organic group having at least one phosphoricacid group at its terminal, B¹ is R^(F1)—O—, D¹-Q¹-O—CH₂— or A²-O—,wherein R^(F1) is a C₁₋₆ perfluoroalkyl group, D¹ is CF₃— or CF₃—O—, Q¹is a C₁₋₂₀ fluoroalkylene group containing at least one hydrogen atom, aC₂₋₂₀ fluoroalkylene group containing at least one hydrogen atom andhaving an etheric oxygen atom between carbon-carbon atoms, a C₁₋₂₀alkylene group, or a C₂₋₂₀ alkylene group having an etheric oxygen atombetween carbon-carbon atoms, and A² is a monovalent organic group havingat least one phosphoric acid group at its terminal, m is an integer offrom 1 to 6, andn1 is an integer of from 1 to 200, provided that when n1 is at least 2,(C_(m)F_(2m)O)_(n1) may be one composed of at least two types of(C_(m)F_(2m)O) different in m.[3] The surface treatment agent according to [2], wherein said(C_(m)F_(2m)O)_(n1) is a group represented by the following formula(2-1):

(C_(r)F_(2r)O)_(n2)(C_(s)F_(2s)O)_(n3)  (2-1)

wherein r is an integer of from 1 to 3, s is an integer of from 3 to 6,provided that r and s are not 3 at the same time, n2 is an integer of atleast 1, n3 is an integer of at least 1, provided that n2+n3 is aninteger of from 2 to 200, and a bonding order of (C_(r)F_(2r)O) and(C_(s)F_(2s)O) is not limited.[4] The surface treatment agent according to [2], wherein said(C_(m)F_(2m)O)_(n1) is a group represented by the following formula(2-2):

(CF₂O)_(n7)(CF₂CF₂O)_(n8)  (2-2)

wherein n7 is an integer of at least 1, n8 is an integer of at least 1,provided that n7+n8 is an integer of from 2 to 200, and a bonding orderof (CF₂O) and (CF₂CF₂O) is not limited.[5] The surface treatment agent according to any one of [2] to [4],wherein said A¹ is a group represented by the following formula (3):

-Q^(F1)(CX₂)_(w1)-E¹-Y¹—O—P(═O)(OH)₂  (3)

wherein Q^(F1) is a C₁₋₂₀ perfluoroalkylene group, CX₂ is CH₂ or CHF, w1is 0 or 1, E¹ is a single bond, —C(═O)NH— (provided that Y¹ is bonded toN), —OC(═O)NH— (provided that Y¹ is bonded to N), —O—, —C(═O)O—(provided that Y¹ is bonded to O), —OC(═O)O—, —NHC(═O)NH— or —NHC(═O)O—(provided that Y¹ is bonded to O), wherein Y¹ is an alkylene group, apoly(oxyalkylene)-alkylene group, a cycloalkylene group, an arylenegroup, or an alkylene group in which at least one of hydrogen atoms issubstituted by a hydroxy group, provided that E¹ is not —O—, —OC(═O)NH—or —OC(═O)O— when w1 is 0, and Y¹ is not an alkylene group when w1 is 1,CX₂ is CH₂ and E¹ is a single bond.[6] The surface treatment agent according to any one of [2] to [5],wherein said Q¹ is a group represented by the following formula (4-1),(4-2) or (4-3):

-Q^(F2)-O—CHFCF₂—  (4-1)

-Q^(F2)-CHFCF₂—  (4-2)

-Q^(F2)-C_(z)H_(2z)—  (4-3)

wherein Q^(F2) is a single bond, a C₁₋₁₅ perfluoroalkylene group, or aC₂₋₁₅ perfluoroalkylene group having an etheric oxygen atom betweencarbon-carbon atoms, Q^(F2) is bonded to said D¹, and z is an integer offrom 1 to 4, provided that Q^(F2) is not a single bond in the formula(4-1) and (4-2) when said D¹ is CF₃—O—.[7] The surface treatment agent according to any one of [2] to [6],wherein the number average molecular weight (Mn) of the compoundrepresented by the formula (1) is 2,000 to 10,000.[8] The surface treatment agent according to any one of [2] to [7],which contains the compound represented by the formula (1) wherein saidB¹ is R^(F1)—O— or D¹-Q¹-O—CH₂—.[9] The surface treatment agent according to any one of [2] to [7],which contains the compound represented by the formula (1) wherein saidB¹ is R^(F1)—O— or D¹-Q¹-O—CH₂— and the compound represented by theformula (1) wherein said B¹ is A²-O—.[10] The surface treatment agent according to [9], wherein the contentof the compound represented by the formula (1) wherein said B¹ is A²-O—,is from 10 to 60 parts by mass, per 100 parts by mass in total of thecompound represented by the formula (1) wherein said B¹ is R^(F1)—O— orD¹-Q¹-O—CH₂—.[11] The surface treatment agent according to any one of [1] to [10],wherein said substrate is a sapphire substrate.[12] A coating agent comprising the surface treatment agent as definedin any one of [1] to [11] and a liquid medium.[13] A substrate having a surface layer formed from the surfacetreatment agent as defined in any one of [1] to [11] or the coatingagent as defined in [12].[14] A compound represented by the following formula (1):

B¹—(C_(m)F_(2m)O)_(n1)-A¹  (1)

wherein A¹ is a monovalent organic group having at least one phosphoricacid group at its terminal, B¹ is R^(F1)—O—, D¹-Q¹-O—CH₂— or A²-O—,wherein R^(F1) is a C₁₋₆ perfluoroalkyl group, D¹ is CF₃— or CF₃—O—, Q¹is a C₁₋₂₀ fluoroalkylene group containing at least one hydrogen atom, aC₂₋₂₀ fluoroalkylene group containing at least one hydrogen atom andhaving an etheric oxygen atom between carbon-carbon atoms, a C₁₋₂₀alkylene group, or a C₂₋₂₀ alkylene group having an etheric oxygen atombetween carbon-carbon atoms, A² is a monovalent organic group having atleast one phosphoric acid group at its terminal,m is an integer of from 1 to 6, andn1 is an integer of from 1 to 200, provided that when n1 is at least 2,(C_(m)F_(2m)O)_(n1) may be one composed of at least two types of(C_(m)F_(2m)O) different in m.

Advantageous Effects of Invention

According to the surface treatment agent of the present invention, it ispossible to impart excellent water/oil repellency, fingerprint stainremovability, abrasion resistance and lubricity, to the substratesurface.

DETAILED DESCRIPTION OF INVENTION Definition of Terms

In this specification, a compound represented by the formula (1) will bealso referred to as compound (1). The same applies to compoundsrepresented by other formulae.

The following definitions of terms will be applied to the entirespecification including the claims.

An “etheric oxygen atom” means an oxygen atom to form an ether bond(—O—) between carbon-carbon atoms.

A “perfluoroalkyl group” means a group having all of hydrogen atoms inan alkyl group substituted by fluorine atoms.

A “fluoroalkylene group” means a group having some or all of hydrogenatoms in an alkylene group substituted by fluorine atoms, and a“perfluoroalkylene group” means a group having all of hydrogen atoms inan alkylene group substituted by fluorine atoms. Here, a “fluoroalkylenegroup” includes a “perfluoroalkylene group”.

A “perfluoropolyether” means a group formed of at least twooxyperfluoroalkylene units. Here, the chemical formula ofoxyperfluoroalkylene represents one having its oxygen atom arranged onthe right side of a perfluoroalkylene group.

A “phosphoric acid group” means —O—P(═O)(OH)₂.

An “organic group” means a group having at least one carbon atom.

A “perfluoropolyether group-containing phosphate compound” means acompound having a perfluoropolyether group and a phosphoric acid group.

A “surface layer” means a layer to be formed on the substrate surface bytreating the substrate surface with the surface treatment agent of thepresent invention. The “surface layer” is present for impartingexcellent water/oil repellency, fingerprint stain removability, abrasionresistance and lubricity to the substrate surface.

[Perfluoropolyether Group-Containing Phosphate Compound]

The surface treatment agent of the present invention (hereinafter alsoreferred to as “the present surface treatment agent”) contains aperfluoropolyether group-containing phosphate compound (hereinafter alsoreferred to as “the present compound”). The present surface treatmentagent may contain one type of the present compound or at least two typesof the present compound.

The present compound, which has a perfluoropolyether group, can impartexcellent water/oil repellency, fingerprint stain removability andlubricity to the substrate surface, when used as the present surfacetreatment agent containing the present compound. Further, when used asthe present surface treatment agent containing the present compound, itcan impart excellent abrasion resistance to the substrate surface,whereby it is possible to suppress deterioration of water/oil repellencydue to abrasion even if the substrate surface is repeatedly rubbed.Here, at least two oxyperfluoroalkylene units composing theperfluoropolyether group may be the same or different. Further, eachoxyperfluoroalkylene unit may be linear or branched, but is preferablylinear since it is possible to impart more excellent oil repellency tothe substrate surface.

The present compound is a compound in which an organic group having atleast one phosphoric acid group bonded to only one terminal of theperfluoropolyether group, or a compound having organic groups eachhaving at least one phosphoric acid group bonded to both terminals ofthe perfluoropolyether group. The present surface treatment agentpreferably contains, as an essential component, the present compoundhaving an organic group having at least one phosphoric acid group bondedto only one terminal of the perfluoropolyether group, since one terminalof the perfluoropolyether group becomes a free terminal which impartsexcellent fingerprint stain removability to the substrate surface.Accordingly, the present surface treatment agent is particularlypreferably one containing the present compound having an organic grouphaving at least one phosphoric acid group bonded to only one terminal ofthe perfluoropolyether group, or one containing a mixture of the presentcompound having an organic group having at least one phosphoric acidgroup bonded to only one terminal of the perfluoropolyether group withthe present compound having organic groups each having at least onephosphoric acid group bonded to both terminals of the perfluoropolyethergroup.

(Compound (1))

Specifically, the present compound is preferably a compound representedby the formula (1):

B¹—(C_(m)F_(2m)O)_(n1)-A¹  (1)

wherein A¹ is a monovalent organic group having at least one phosphoricacid group at its terminal, B¹ is R^(F1)—O—, D¹-Q¹-O—CH₂— or A²-O—,wherein R^(F1) is a C₁₋₆ perfluoroalkyl group, D¹ is CF₃— or CF₃—O—, Q¹is a C₁₋₂₀ fluoroalkylene group containing at least one hydrogen atom, aC₂₋₂₀ fluoroalkylene group containing at least one hydrogen atom andhaving an etheric oxygen atom between carbon-carbon atoms, a C₁₋₂₀alkylene group, or a C₂₋₂₀ alkylene group having an etheric oxygen atombetween carbon-carbon atoms, and A² is a monovalent organic group havingat least one phosphoric acid group at its terminal,m is an integer of from 1 to 6, andn1 is an integer of from 1 to 200, provided that when n1 is at least 2,(C_(m)F_(2m)O)_(n1) may be one composed of at least two types of(C_(m)F_(2m)O) different in m.<(C_(m)F_(2m)O)_(n1)>

(C_(m)F_(2m)O)_(n1) is a perfluoropolyether group. Therefore, by usingcompound (1), it is possible to impart excellent water/oil repellency,fingerprint stain removability and lubricity to the substrate surface.

m is an integer of from 1 to 6. (C_(m)F_(2m)O) may be linear orbranched. (C_(m)F_(2m)O) may, for example, be (CF₂O), (CF₂CF₂O),(CF(CF₃)O), (CF₂CF₂CF₂O), (CF(CF₃)CF₂O), (CF₂CF(CF₃)O), (CF₂CF₂CF₂CF₂O),(CF(CF₃)CF₂CF₂O), (CF₂CF(CF₃)CF₃O) or (CF₂CF₂CF(CF₃)O).

With a view to imparting excellent water/oil repellency, fingerprintstain removability and lubricity to the substrate surface, n1 is ainteger of at least 2, preferably an integer of at least 4, particularlypreferably an integer of at least 5. With a view to imparting moreexcellent abrasion resistance to the substrate surface, and further witha view to exhibiting excellent compatibility when other components areblended into the present surface treatment agent, n1 is preferably aninteger of at most 100, more preferably an integer of at most 80,particularly preferably an integer of at most 60. When the presentsurface treatment agent contains at least two types of compound (1), n1is an average value. In such a case, n1 may not be an integer.

When n1 is at least 2, (C_(m)F_(2m)O)_(n1) may be one composed of atleast two types of C_(m)F_(2m)O different in m. In such a case, abonding order of C_(m)F_(2m)O is not restricted. For example, in a casewhere CF₂O (m is 1) and CF₂CF₂O (m is 2) are present, CF₂O and CF₂CF₂Omay be randomly arranged, CF₂O and CF₂CF₂O may be alternately arranged,or a block composed of a plurality of CF₂O and a block composed of aplurality of CF₂CF₂O may be linked.

<<Preferable First (C_(m)F_(2m)O)_(n1)>>

(C_(m)F_(2m)O)_(n1) is preferably a group represented by the followingformula (2-1) with a view to imparting more excellent water/oilrepellency and abrasion resistance to the substrate surface.

(C_(r)F_(2r)O)_(n2)(C_(s)F_(2s)O)_(n3)  (2-1)

wherein r is an integer of from 1 to 3, s is an integer of from 3 to 6,provided that r and s are not 3 at the same time, n2 is an integer of atleast 1, n3 is an integer of at least 1, provided that n2+n3 is aninteger of from 2 to 200, and a bonding order of (C_(r)F_(2r)O) and(C_(s)F_(2s)O) is not limited.

With a view to imparting more excellent fingerprint stain removabilityto the substrate surface, n2 is preferably an integer of at least 3,particularly preferably an integer of at least 5. With a view toexhibiting excellent compatibility when other components are blendedinto the present surface treatment agent, n2 is preferably an integer ofat most 20, particularly preferably an integer of at most 10.

With a view to imparting more excellent water/oil repellency to thesubstrate surface, n3 is preferably an integer of at least 3,particularly preferably an integer of at least 5. With a view toexhibiting excellent compatibility when other components are blendedinto the present surface treatment agent, n3 is preferably an integer ofat most 20, particularly preferably an integer of at most 10.

With a view to imparting more excellent abrasion resistance to thesubstrate surface while the number of phosphoric acid groups present perunit molecular weight of compound (1) would not be too small, andfurther with a view to exhibiting excellent compatibility when othercomponents are blended into the present surface treatment agent, n2+n3is preferably an integer of from 2 to 100, more preferably an integer offrom 2 to 40, particularly preferably an integer of from 2 to 20.

Further, with a view to imparting more excellent water/oil repellencyand abrasion resistance to the substrate surface, preferred is a groupof the formula (2-1) wherein r is 2 and s is 4, more preferred is agroup represented by the following formula (2-1-a), particularlypreferred is a group represented by the following formula (2-1-b):

(C₂F₄O)_(n4)(C₄F₈O)_(n5)  (2-1-a)

wherein n4 is an integer of at least 1, n5 is an integer of at least 1,provided that n4+n5 is an integer of from 2 to 200, and (C₂F₄O) and(C₄F₈O) are alternately arranged.

[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]  (2-1-b)

wherein n6 is an integer of from 1 to 99.

n6 is preferably an integer of from 1 to 20, particularly preferably aninteger of from 1 to 10.

<<Preferable Second (C_(m)F_(2m)O)_(n1)>>

With a view to imparting more excellent lubricity to the substratesurface, (C_(m)F_(2m)O)_(n1) is preferably a group represented by thefollowing formula (2-2):

(CF₂O)_(n7)(CF₂CF₂O)_(n8)  (2-2)

wherein n7 is an integer of at least 1, n8 is an integer of at least 1,provided that n7+n8 is an integer of from 2 to 200, and a bonding orderof (CF₂O) and (CF₂CF₂O) is not limited.

(CF₂O)_(n7)(CF₂CF₂O)_(n8), which is an oxyperfluoroalkylene group havinga small number of carbon atoms, is excellent in flexibility. Therefore,it is possible to impart more excellent lubricity to the substratesurface. Especially, (CF₂O)_(n7), which is a group having an oxygen atomand a number of carbon atoms being 1, is more excellent in flexibility.

With a view to imparting more excellent water/oil repellency,fingerprint stain removability and lubricity to the substrate surface,n7 is preferably an integer of at least 2, particularly preferably aninteger of at least 3. With a view to imparting more excellent abrasionresistance to the substrate surface while the number of phosphoric acidgroups present per unit molecular weight of compound (1) would not betoo small, and further with a view to exhibiting excellent compatibilitywhen other components are blended into the present surface treatmentagent, n7 is preferably an integer of at most 50, more preferably aninteger of at most 40, particularly preferably an integer of at most 30.

With a view to imparting more excellent water/oil repellency,fingerprint stain removability and lubricity to the substrate surface,n8 is preferably an integer of at least 2. With a view to imparting moreexcellent abrasion resistance to the substrate surface while the numberof phosphoric acid groups present per unit molecular weight of compound(1) would not be too small, and further with a view to exhibitingexcellent compatibility when other components are blended into thepresent surface treatment agent, n8 is preferably an integer of at most50, more preferably an integer of at most 40, particularly preferably aninteger of at most 30.

n7+n8 is preferably an integer of from 2 to 100, more preferably aninteger of from 2 to 80, particularly preferably an integer of from 2 to60.

Further, with a view to imparting more excellent lubricity to thesubstrate surface, the ratio of n7 to n8 is preferably more than 0 timeand at most three times, particularly preferably from 1 to 2 times.

<A¹>

A¹ is a monovalent organic group having at least one phosphoric acidgroup at its terminal. Since A¹ has a phosphoric acid group, by usingcompound (1), it is possible to impart excellent water/oil repellency,fingerprint stain removability and abrasion resistance to the substratesurface.

The number of phosphoric acid groups in A¹ is from 1 to 3, preferably 1or 2, particularly preferably 1.

When the number of phosphoric acid groups is 1, A¹ is preferably a grouprepresented by the following formula (3):

-Q^(F1)(CX₂)_(w1)-E¹-Y¹—O—P(═O)(OH)₂  (3)

wherein Q^(F1) is a C₁₋₂₀ perfluoroalkylene group, CX₂ is CH₂ or CHF, w1is 0 or 1, E¹ is a single bond, —C(═O)NH— (provided that Y¹ is bonded toN), —OC(═O)NH— (provided that Y¹ is bonded to N), —O—, —C(═O)O—(provided that Y¹ is bonded to O), —OC(═O)O—, —NHC(═O)NH— or —NHC(═O)O—(provided that Y¹ is bonded to O),wherein Y¹ is an alkylene group, a poly(oxyalkylene)-alkylene group, acycloalkylene group, an arylene group, or an alkylene group in which atleast one of hydrogen atoms is substituted by a hydroxy group, providedthat E¹ is not —O—, —OC(═O)NH— or —OC(═O)O— when w1 is 0, and Y¹ is notan alkylene group when w1 is 1, CX₂ is CH₂ and E¹ is a single bond.

Q^(F1) is a C₁₋₂₀ perfluoroalkylene group. The perfluoroalkylene groupmay be linear or branched. With a view to imparting excellentfingerprint stain removability to the substrate surface, Q^(F1) ispreferably a C₁₋₆ perfluoroalkylene group, more preferably a C₁₋₃perfluorolalkylene group, particularly preferably the followingperfluoroalkylene group.

—CF₂—, —CF₂CF₂—, —CF₂CF₂CF₂— or —CF(CF₃)—.

Y¹ is an alkylene group, a poly(oxyalkylene)-alkylene group, acycloalkylene group, an arylene group or an alkylene group in which atleast one of hydrogen atoms is substituted by a hydroxy group. Thenumber of carbon atoms of “alkylene” in the alkylene group and thepoly(oxyalkylene)-alkylene group, is preferably from 2 to 6,particularly preferably from 2 to 4. From the viewpoint of easiness ofproduction of compound (1), Y¹ is preferably an alkylene group or apoly(oxyalkylene)-alkylene group.

Y¹ is particularly preferably the following groups, wherein p1 and q1are an integer of from 1 to 20, preferably an integer of from 1 to 10,particularly preferably an integer of from 1 to 3.

—CH₂CH₂—,

—CH₂CH(CH₃)—,

—CH₂CH₂CH₂—,

—CH₂CH₂CH₂CH₂—,

—(CH₂CH₂O)_(p1)—CH₂CH₂— or

—(CH₂CH(CH₃)O)_(q1)—CH₂CH(CH₃)—.

<<Preferred A¹>>

From the viewpoint of easiness of production of compound (1), A¹ isparticularly preferably a group represented by the following formula(3-1) or (3-2). Here, the above preferred examples will be applied toQ^(F1) and Y¹.

-Q^(F1)-C(═O)NH—Y¹—O—P(═O)(OH)₂  (3-1)

-Q^(F1)-CX₂—O—Y¹—O—P(═O)(OH)₂  (3-2)

<B¹>

B¹ is R^(F1)—O—, D-Q¹-O—CH₂— or A²-O—.

The present compound having an organic group having at least onephosphoric acid group bonded to only one terminal of theperfluoropolyether group, is compound (1) wherein B¹ is R^(F1)—O— orD¹-Q¹-O—CH₂—, and the present compound having organic groups each havingat least one phosphoric acid group respectively bonded to both terminalsof the perfluoropolyether group, is compound (1) wherein B¹ is A²-O—.

B¹ is preferably R^(F1)—O— or D¹-Q¹-O—CH₂—. When B¹ is R^(F1)—O— orD¹-Q¹-O—CH₂—, one terminal of compound (1) is CF₃—. Therefore, by usingcompound (1) having R^(F1-)O— or D¹-Q¹-O—CH₂— on the substrate surface,it is possible to impart excellent fingerprint stain removability to thesubstrate surface.

On the other hand, when B¹ is A²-O—, the number of phosphoric acidgroups capable of reacting with a substrate will increase at bothterminals of compound (1), whereby it is possible to impart moreexcellent abrasion resistance to the substrate surface.

<<R^(F1)>>

R^(F1) is a C₁₋₆ perfluoroalkyl group. The perfluoroalkyl group may belinear or branched. As a specific example of R^(F1), CF₃—, CF₃CF₂—,CF₃(CF₂)₂—, CF₃(CF₂)₃—, CF₃(CF₂)₄—, CF₃(CF₂)₅— or CF₃CF(CF₃)— may bementioned. With a view to imparting more excellent water/oil repellencyand fingerprint stain removability to the substrate surface, R^(F1) ispreferably a C₁₋₄ linear perfluoroalkyl group (CF₃—, CF₃CF₂—, CF₃(CF₂)₂—or CF₃(CF₂)₃—).

<<Q¹>>

Q¹ is a C₁₋₂₀ fluoroalkylene group containing at least one hydrogenatom, a C₂₋₂₀ fluoroalkylene group containing at least one hydrogen atomand having an etheric oxygen atom between carbon-carbon atoms, a C₁₋₂₀alkylene group, or a C₂₋₂₀ alkylene group having an etheric oxygen atombetween carbon-carbon atoms. The number of hydrogen atoms in Q¹ is atleast 1, preferably at least 2, particularly preferably at least 3.

Q¹ is preferably a single bond, or a group represented by the followingformula (4-1), (4-2) or (4-3) in view of easiness of production ofcompound (1) wherein B¹ is D¹-Q¹-O—CH₂—.

-Q^(F2)-O—CHFCF₂—  (4-1)

-Q^(F2)-CHFCF₂—  (4-2)

-Q^(F2)-C_(z)H_(2z)—  (4-3)

wherein Q^(F2) is a single bond, a C₁₋₁₅ perfluoroalkylene group, or aC₂₋₁₅ perfluoroalkylene group having an etheric oxygen atom betweencarbon-carbon atoms, Q^(F2) is bonded to said D¹, and z is an integer offrom 1 to 4, provided that Q^(F2) is not a single bond in the formula(4-1) and (4-2) when said D¹ is CF₃—O—.

With a view to sufficiently imparting fingerprint stain removability orlubricity to the substrate surface, Q^(F2) is preferably a C₁₋₉perfluoroalkylene group or a C₂₋₁₃ perfluoroalkylene group having anetheric oxygen atom between carbon-carbon atoms. Here, theperfluoroalkylene group may be linear or branched. z is preferably aninteger of from 1 to 3, and when z is at least 3, C_(z)H_(2z) may belinear or branched, but is preferably linear.

In a case where Q¹ is a group represented by the formula (4-1), aspecific example of the D¹-Q¹- group includes the following.

CF₃—O—CHFCF₂—,

CF₃—CF₂—O—CHFCF₂—,

CF₃—CF₂CF₂—O—CHFCF₂—,

CF₃—CF₂CF₂CF₂—O—CHFCF₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂—O—CHFCF₂—,

CF₃—O—CF₂CF₂—O—CHFCF₂—,

CF₃—CF₂OCF₂CF₂—O—CHFCF₂—,

CF₃—O—CF₂CF₂OCF₂CF₂—O—CHFCF₂—,

CF₃—CF₂OCF₂CF₂OCF₂CF₂—O—CHFCF₂—,

CF₃—CF₂CF₂OCF(CF₃)CF₂—O—CHFCF₂—,

CF₃—CF₂CF₂OCF(CF₃)CF₂OCF(CF₃)CF₂—O—CHFCF₂—.

In a case where Q¹ is a group represented by the formula (4-2), aspecific example of the D¹-Q¹- group includes the following.

CF₃—CHFCF₂—,

CF₃—CF₂—CHFCF₂—,

CF₃—CF₂CF₂—CHFCF₂—,

CF₃—CF₂CF₂CF₂—CHFCF₂—.

In a case where Q¹ is a group represented by the formula (4-3), aspecific example of the D¹-Q¹- group includes the following.

CF₃—CH₂—,

CF₃—CF₂—CH₂—,

CF₃—CF₂CF₂—CH₂—,

CF₃—CF₂CF₂CF₂—CH₂—,

CF₃—CF₂CF₂CF₂CF₂—CH₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂—CH₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂CF₂—CH₂—,

CF₃—CH₂CH₂—,

CF₃—CF₂—CH₂CH₂—,

CF₃—CF₂CF₂—CH₂CH₂—,

CF₃—CF₂CF₂CF₂—CH₂CH₂—,

CF₃—CF₂CF₂CF₂CF₂—CH₂CH₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂—CH₂CH₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂CF₂—CH₂CH₂—,

CF₃—CH₂CH₂CH₂—,

CF₃—CF₂—CH₂CH₂CH₂—,

CF₃—CF₂CF₂—CH₂CH₂CH₂—,

CF₃—CF₂CF₂CF₂—CH₂CH₂CH₂—,

CF₃—CF₂CF₂CF₂CF₂—CH₂CH₂CH₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂—CH₂CH₂CH₂—,

CF₃—CF₂CF₂CF₂CF₂CF₂CF₂—CH₂CH₂CH₂—,

CF₃—O—CF₂—CH₂—,

CF₃—CF₂OCF₂—CH₂—,

CF₃—O—CF₂CF₂OCF₂—CH₂—,

CF₃—CF₂OCF₂CF₂OCF₂—CH₂—,

CF₃—O—CF₂CF₂OCF₂CF₂OCF₂—CH₂—,

CF₃—CF₂OCF₂CF₂CF₂CF₂CF₂—CH₂—.

Q¹ is preferably a group represented by the formula (4-1) in view ofeasiness of production of compound (1) wherein B¹ is D¹-Q¹-O—CH₂—, andthe D¹-Q¹- group is preferably CF₃—CF₂CF₂—O—CHFCF₂— orCF₃—CF₂CF₂CF₂CF₂CF₂—O—CHFCF₂—, particularly preferablyCF₃—CF₂CF₂—O—CHFCF₂—.

<A²>

A² is a monovalent organic group having at least one phosphoric acidgroup at its terminal. The above description relating to A¹ includingpreferred examples, will be also applied to examples of A².

Preferred Embodiments of Compound (1)

Compound (1) wherein B¹ is R^(F1)—O— is preferably the followingcompound (1a-1). Further, compound (1) wherein B¹ is D¹-Q¹-O—CH₂— ispreferably the following compound (1a-2).

<Compound (1a-1)>

R^(F2)—O—[(C₂F₄O)_(n9)(C₄F₈O)_(n10)]-A³  (1a-1)

wherein n9 is an integer of at least 1, n10 is an integer of at least 1,provided that n9+n10 is an integer of from 2 to 200, (C₂F₄O) and (C₄F₈O)are alternately arranged, R^(F2) is a C₁₋₆ perfluoroalkyl group, and A³is a monovalent organic group having at least one phosphoric acid groupat its terminal.

By using compound (1a-1), the present surface treatment agent can impartmore excellent water/oil repellency to the substrate surface.

With a view to imparting more excellent water/oil repellency to thesubstrate surface, (C₂F₄O) and (C₄F₈O) are preferably (CF₂CF₂O) and(CF₂CF₂CF₂CF₂O).

The above description relating to n2 including preferred examples, willbe also applied to n9.

The above description relating to n3 including preferred examples, willbe also applied to n10.

With a view to imparting more excellent water/oil repellency andabrasion resistance to the substrate surface,[(C₂F₄O)_(n9)(C₄F₈O)_(n10)] is preferably a group represented by theabove formula (2-1-b).

The above description relating to R^(F1) including preferred examples,will be also applied to examples of R^(F2). With a view to impartingmore excellent fingerprint stain removability to the substrate surface,R^(F2) is particularly preferably CF₃— or CF₃CF₂—.

The above description relating to A¹ including preferred examples, willbe also applied to examples of A³. A³ is particularly preferably a grouprepresented by the formula (3-1).

With a view to imparting particularly excellent water/oil repellency andabrasion resistance to the substrate surface, compound (1a-1) ispreferably a compound (1a-1-1).

CF₃—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n11)—CF₂CF₂O]—CF₂CF₂CF₂—C(═O)NH—CH₂CH₂—O—P(═O)(OH)₂  (1a-1-1)

wherein n11 is an integer of from 1 to 99.

The above description relating to n6 including preferred examples, willbe also applied to n11.

<Compound (1a-2)>

D²-Q²-O—CH₂—(C_(v)F_(2v)O)_(n12)-A⁴  (1a-2)

wherein D² is CF₃— or CF₃—O—, and Q² is a C₁₋₂₀ fluoroalkylene groupcontaining at least one hydrogen atom, a C₂₋₂₀ fluoroalkylene groupcontaining at least one hydrogen atom and having an etheric oxygen atombetween carbon-carbon atoms, a C₁₋₂₀ alkylene group, or a C₂₋₂₀ alkylenegroup having an etheric oxygen atom between carbon-carbon atoms, v is aninteger of from 1 to 6, n12 is an integer of from 1 to 200, providedthat when n12 is at least 2, (C_(v)F_(2v)O)_(n12) may be one composed ofat least two types of (C_(v)F_(2v)O) different in v, and A⁴ is amonovalent organic group having at least one phosphoric acid group atits terminal.

Compound (1a-2), which contains a CH₂ group (the CH₂ group is moreimproved in flexibility than a CF₂ group) having hydrogen atoms with asmall atomic radius in its molecule, is more improved in flexibility.Therefore, the present surface treatment agent, which uses compound(1a-2), can impart more excellent abrasion resistance and lubricity tothe substrate surface.

The above description relating to (C_(m)F_(2m)O)_(n1) includingpreferred examples, will be also applied to examples of(C_(v)F_(2v)O)_(n12), and (C_(v)F_(2v)O)_(n12) is particularlypreferably a preferable second (C_(m)F_(2m)O)_(n1).

The above description relating to Q¹ including preferred examples, willbe also applied to examples of Q², provided that when Q² is a grouprepresented by the formula (4-1), (4-2) or (4-3), Q^(F2) in the formula(4-1), (4-2) or (4-3) is bonded to D², and further when D² is CF₃—O—,Q^(F2) in the formula (4-1) or (4-2) is not a single bond.

The above description relating to A¹ including preferred examples, willbe also applied to examples of A⁴. A⁴ is particularly preferably a grouprepresented by the formula (3-2).

With a view to imparting particularly excellent abrasion resistance andlubricity to the substrate surface, compound (1a-2) is preferablycompound (1a-2-1).

CF₃—CF₂CF₂OCHFCF₂—O—CH₂—CF₂O[(CF₂)_(n13-1)(CF₂CF₂O)_(n14)]CF₂CH₂—O—(CH₂CH₂O)_(p3)—CH₂CH₂—O—P(═O)(OH)₂  (1a-2-1)

wherein n13 is an integer of at least 1, n14 is an integer of at least1, provided that n13+n14 is an integer of from 2 to 200, the bondingorder of (CF₂O) and (CF₂CF₂O) is not limited, and p3 is an integer of 0or 1 to 20.

The above description relating to p2 including preferred examples, willbe also applied to p3.

The number average molecular weight (Mn) of the present compound ispreferably from 2,000 to 10,000, more preferably from 2,500 to 8,000,particularly preferably from 3,000 to 6,000. When it is within the aboverange, excellent water/oil repellency, fingerprint stain removabilityand lubricity can be imparted to the substrate surface, and further,compatibility with other components can be excellent when such othercomponents are blended into the present surface treatment agent.

The number average molecular weight of the present compound iscalculated by the following method by means of NMR analysis.

The number average molecular weight is calculated by determining thenumber (average value) of oxyperfluoroalkylene groups based on theterminal group, by means of ¹H-NMR or ¹⁹F-NMR. The terminal group is,for example, B¹ or A¹ in the formula (1).

[Process for Producing Compound (1)]

A process for producing compound (1) will be explained, with referenceto the compounds represented by the formula (1a-1-2) and the formula(1a-2-2).

(Process for Producing Compound (1a-1-2))

R^(F1)—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂)_(n6)CF₂CF₂O]—CF₂CF₂CF₂—C(═O)NH—Y¹—O—P(═O)(OH)₂  (1a-1-2)

Compound (12a) is subjected to hydrogen reduction by using a reducingagent (such as sodium borohydride or lithium aluminum hydride) to obtaincompound (11a).

CF₂═CFO—CF₂CF₂CF₂C(═O)OCH₃  (12a)

CF₂═CFO—CF₂CF₂CF₂CH₂OH  (11a)

Compound (11a) and an alcohol (such as methanol, ethanol, 1-propanol,2-propanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol or1,1,1,3,3,3-hexafluoro-2-propanol, hereinafter referred to as R^(f1)—OH,wherein R^(f1) is a C₁₋₆ fluoroalkyl group or a C₁₋₆ alkyl group) arereacted in the presence of a base or a quaternary ammonium salt (such aspotassium carbonate, sodium carbonate, sodium fluoride, potassiumfluoride, cesium fluoride, sodium hydride, potassium tert-butoxide,sodium hydroxide, potassium hydroxide, tetrabutylammonium chloride ortetrabutylammonium bromide) to obtain compound (10a).

R^(f1)—O—(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(n6+1)—H  (10a)

By controlling the amount of R^(f1)—OH to be added to compound (11a), itis possible to synthesize compound (10a) having a desired number averagemolecular weight. Further, R^(f1)—OH may be compound (11a) itself, andby controlling the reaction time or by separation-purification of theproduct, it is possible to synthesize compound (10a) having a desirednumber average molecular weight.

The synthesis of compound (11a) and the synthesis of compound (10a) bythe polyaddition reaction can be carried out by a known method disclosedin U.S. Pat. No. 5,134,211.

Compound (10a) and ClC(═O)R¹ are subjected to an esterification reactionto obtain compound (9a). Here, R¹ is a C₁₋₁₁ alkyl group, a C₁₋₁₁fluoroalkyl group, a C₂₋₁₁ alkyl group having an etheric oxygen atombetween carbon-carbon atoms or a C₂₋₁₁ fluoroalkyl group having anetheric oxygen atom between carbon-carbon atoms. The fluoroalkyl groupis preferably a perfluoroalkyl group.

R^(f1)—O—(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(n6+1)—C(═O)R¹  (9a)

Further, by means of fluorine gas, hydrogen atoms in compound (9a) aresubstituted by fluorine atoms to obtain compound (7a). Here, when R¹ isa group having a hydrogen atom, R^(F4) is a group having all of thehydrogen atoms contained in R¹ substituted by fluorine atoms, and whenR¹ is a group having no hydrogen atoms, R^(F4) is the same group as R¹,which is a C₁₋₁₁ perfluoroalkyl group or a C₂₋₁₁ perfluoroalkyl grouphaving an etheric oxygen atom between carbon-carbon atoms. R^(F1) is agroup having all of the hydrogen atoms contained in R¹ substituted byfluorine atoms. Such a fluorination step can be carried out, forexample, in accordance with a method disclosed in WO2000/56694.

R^(F1)—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂CF₂—C(═O)R^(F4)  (7a)

Compound (7a) and an alcohol (such as methanol, ethanol, 1-propanol or2-propanol, hereinafter referred to as R²OH, wherein R² is an alkylgroup) are reacted to obtain compound (6a) represented by the followingformula (6a).

R^(F1)—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂C(═O)OR²  (6a)

Compound (6a) and H₂N—Y¹—OH are reacted to obtain compound (5a).

R^(F1)—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂—C(═O)NH—Y¹—OH  (5a)

Compound (5a) and phosphorus oxychloride or diphosphorus pentoxide arereacted, followed by hydrolysis to obtain compound (1a-1-1).

Further, it is also possible to obtain compound (1a-1-1) by reactingcompound (6a) with NH₂—Y¹—OP(═O)(OH)₂.

(Process for Producing Compound (1a-2-2))

D¹-Q^(F2)-O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—(CH₂CH₂O)_(p2)—CH₂CH₂—O—P(═O)(OH)₂  (1a-2-2)

wherein p2 is an integer of 0 or 1 to 20. p2 is preferably an integer of0 or 1 to 10, particularly preferably an integer of 0 or 1 to 3.

In the presence of a basic compound, D¹-Q^(F2)-O—CF═CF₂ is reacted withcompound (4a-2) having OH groups at both terminals to obtain a mixtureof compound (3a-2), compound (3a-2-2) and unreacted compound (4a-2).

HOCH₂—CF₂O[(CF₂)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂OH  (4a-2)

D¹-Q^(F2)-O—CHFCF₂—O—CH₂—CF₂O[(CF₂)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂OH  (3a-2)

D¹-Q^(F2)-O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—CF₂CHF—O-Q^(F2)-D¹  (3a-2-2)

From the above mixture, the monofunctional compound (3a-2) having a OHgroup remaining at its one terminal, is isolated, and in the presence ofa basic compound such as cesium carbonate, ethylene carbonate is addedto compound (3a-2) while conducting decarboxylation, to obtain compound(2a-2).

D¹-Q^(F2)-O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—(CH₂CH₂O)_(p2)—CH₂CH₂—OH  (2a-2)

Compound (2a-2) and phosphorus oxychloride or diphosphorus pentoxide arereacted, followed by hydrolysis to obtain compound (1a-2-2).

D¹-Q^(F2)-O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—(CH₂CH₂O)_(p2)—CH₂CH₂—O—P(═O)(OH)₂  (1a-2-2)

[Surface Treatment Agent]

The present surface treatment agent contains the present compound. Thepresent surface treatment agent may be composed solely of the presentcompound. Here, the present compound is preferably compound (1) whereinB¹ is R^(F1)—O— or D¹-Q¹-O—CH₂—, or a mixture of compound (1) wherein B¹is R^(F1)—O— or D¹-Q¹-O—CH₂— and compound (1) wherein B¹ is A²-O—. Thepresent surface treatment agent may contain compounds (hereinafterreferred to also as impurities) which are included inevitably in theproduction of the present compound. The present surface treatment agentmay contain other components other than the present compound andimpurities.

(Other Components)

Other components may, for example, be a perfluoropolyether compoundhaving no phosphoric acid groups (hereinafter referred to also as afluorinated ether compound) or a catalyst.

<Fluorinated Ether Compound>

The fluorinated ether compound may, for example, be a compound producedin the production step of compound (1) as a by-product or a known(especially, commercially available) compound to be used in the sameapplication as compound (1). The fluorinated ether compound ispreferably the following compound (7) or compound (8).

<<Compound (7)>>

Compound (7) is a fluorinated ether compound represented by thefollowing formula (7).

R^(F5)—O—(C_(p)F_(2p)O)_(n15)—R^(F6)  (7)

wherein R^(F5) and R^(F6) are each independently a C₁₋₆ perfluoroalkylgroup, p is an integer of from 1 to 6, and n15 is an integer of from 1to 200, provided that when n15 is at least 2, (C_(p)F_(2p)O)_(q) may beone composed of at least two types of C_(p)F_(2p)O different in p.

The above description relating to R^(F1) including the preferredexamples, will be also applied to examples of R^(F5) and R^(F6).

The above description relating to (C_(m)F_(2m)O)_(n1) including thepreferred examples, will be also applied to examples of(C_(p)F_(2p)O)_(n15). (C_(p)F₂O)_(n15) is preferably the same as(C_(m)F_(2m)O)_(n1) in the formula (1) with a view to effectively usingthe compound produced as a by-product in the production step of compound(1). For example, in a case where compound (1) is a compound having[(CF₂O)_(n4)(CF₂CF₂O)_(n5)], it is particularly preferred that compound(7) is also a compound having [(CF₂O)_(n4)(CF₂CF₂O)_(n5)].

As compound (7), a commercially available product may be used. As acommercial product, FOMBLIN M, FOMBLIN Y, FOMBLIN Z (manufactured bySolvay Solexis K.K.), Krytox (manufactured by DuPont), DEMNUM(manufactured by DAIKIN INDUSTRIES, LTD.) may, for example, bementioned.

<<Compound (8)>>

Compound (8) is a fluorinated ether compound represented by thefollowing formula (8).

D³-Q³-O—CH₂—(C_(q)F_(2q)O)_(n16)—C_(t)F_(2t)—CH₂—O-Q⁴-D⁴  (8)

wherein D³ and D⁴ are each independently CF₃— or CF₃—O—, Q³ and Q⁴ areeach independently a C₁₋₂₀ fluoroalkylene group containing at least onehydrogen atom, a C₂₋₂₀ fluoroalkylene group containing at least onehydrogen atom and having an etheric oxygen atom between carbon-carbonatoms, a C₁₋₂₀ alkylene group, or a C₂₋₂₀ alkylene group having anetheric oxygen atom between carbon-carbon atoms, t is an integer of from1 to 5, q is an integer of from 1 to 6, n16 is an integer of from 1 to200, provided that when n16 is at least 2, (C_(q)F_(2q)O)_(n16) may beone composed of at least two types of (C_(q)F_(2q)O) different in q.

The above description relating to Q¹ including the preferred examples,will be also applied to examples of Q³ and Q⁴. When Q³ and Q⁴ are agroup represented by the formula (6-1), the formula (6-2) or the formula(6-3), Q^(F2) is bonded to D³ in Q³, and Q^(F2) is bonded to D⁴ in Q⁴,provided that when D³ is CF₃—O—, Q^(F2) is not a single bond in theformula (6-1) and the formula (6-2), and further when D⁴ is CF₃—O—,Q^(F2) is not a single bond in the formula (6-1) or the formula (6-2).

The above description relating to (C_(m)F_(2m)O)_(n1) including thepreferred examples, will be also applied to examples of(C_(q)F_(2q)O)_(n16). (C_(q)F_(2q)O)_(n16) is preferably the same as(C_(m)F_(2m)O)_(n1) in the formula (1) with a view to effectively usingthe compound (such as compound (3a-2-2)) produced as a by-product in theproduction step of compound (1).

As specific examples of compound (8), the compounds represented by thefollowing formulae are mentioned, wherein the two Q^(F2) groups may bethe same or different.

D³-Q^(F2)-O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—CF₂CHF—O-Q^(F2)-D⁴,

D³-Q^(F2)-CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n4-1)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—CF₂CHF-Q^(F2)-D⁴,

D³-Q^(F2)-C_(z)H_(2z)—O—CH₂—CF₂O[(CF₂O)_(n41)(CF₂CF₂O)_(n5)]—CF₂CH₂—O—C_(z)H_(2z)-Q^(F2)-D⁴.

<Catalyst>

The catalyst may, for example, be an acid catalyst or a basic catalyst,which promotes hydrolysis and a condensation reaction of a hydroxy groupin the phosphoric acid group of the present compound. The acid catalystmay, for example, be hydrochloric acid, nitric acid, acetic acid,sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid orp-toluenesulfonic acid. The basic catalyst may, for example, be sodiumhydroxide, potassium hydroxide or ammonia.

(Composition)

In a case where the present compound in the present surface treatmentagent is a mixture of compound (1) wherein B¹ is R^(F1)—O— orD¹-Q¹-O—CH₂— and compound (1) wherein B¹ is A²-O—, the content ofcompound (1) wherein B¹ is A²-O— is preferably from 10 to 60 parts bymass, particularly preferably from 20 to 50 parts by mass, per 100 partsby mass in total of compound (1) wherein B¹ is R^(F1)—O— orD¹-Q¹-O—CH₂—. When the content of compound (1) wherein B¹ is A²-O— is atleast the lower limit value of the above range, it is possible to impartexcellent abrasion resistance to the substrate surface, and when thecontent is at most the upper limit value of the above range, it ispossible to impart excellent water/oil repellency, fingerprint stainremovability and lubricity to the substrate surface.

In the present surface treatment agent, the content of the fluorinatedether compound is preferably at most 30 mass %, particularly preferablyat most 20 mass %.

In the present surface treatment agent, the content of the catalyst ispreferably at most 10 mass %, particularly preferably at most 1 mass %.

In the present surface treatment agent, the content of other componentsother than the fluorinated ether compound and the catalyst is preferablyat most 10 mass %, particularly preferably at most 1 mass %.

[Coating Liquid]

The coating liquid of the present invention (hereinafter referred toalso as the present coating liquid) contains the present surfacetreatment agent and a liquid medium. The present coating liquid is notparticularly limited so long as it is in a liquid form, and it may be asolution or a dispersion.

The solid content concentration in the present coating liquid ispreferably from 0.001 to 10 mass %, particularly preferably from 0.01 to1 mass %. The solid content concentration of the present coating liquidis a value calculated from the mass of the present surface treatmentagent before heating and the mass after heating by a convection dryer at120° C. for 4 hours.

The concentration of the present compound in the present coating liquidis preferably from 0.001 to 10 mass %, particularly preferably from 0.1to 1 mass %.

(Liquid Medium)

The liquid medium is preferably an organic solvent. The organic solventmay be a fluorinated organic solvent or a non-fluorinated organicsolvent, or both solvents may be used in combination. The amount of theliquid medium is preferably from 90 to 99.999 mass %, particularlypreferably from 99 to 99.9 mass %, in the present coating liquid.

The fluorinated organic solvent may, for example, be a fluorinatedalkane, a fluorinated aromatic compound, a fluoroalkyl ether, afluorinated alkylamine or a fluoroalcohol, and in view of solubility ofthe present compound, preferred is a fluorinated alkane, a fluorinatedaromatic compound or a fluoroalkyl ether, particularly preferred is afluoroalkyl ether.

As a fluorinated alkane, a C₄₋₈ compound may be mentioned. As acommercial product, C₆F₁₃H (AC-2000: product name, manufactured by AsahiGlass Company, Limited), C₆F₁₃C₂H₅ (AC-6000: product name, manufacturedby Asahi Glass Company, Limited) or C₂F₅CHFCHFCF₃ (Vertrel: productname, manufactured by DuPont) may, for example, be mentioned.

As a fluorinated aromatic compound, hexafluorobenzene,trifluoromethylbenzene, perfluorotoluene or bis(trifluoromethyl)benzenemay, for example, be mentioned.

As a fluoroalkyl ether, a C₄₋₁₂ compound may be mentioned. As acommercial product, CF₃CH₂OCF₂CF₂H (AE-3000: product name, manufacturedby Asahi Glass Company, Limited), C₄F₉OCH₃ (Novec-7100: product name,manufactured by 3M), C₄F₉OC₂H₅(Novec-7200: product name, manufactured by3M) or C₆F₁₃OCH₃ (Novec-7300: product name, manufactured by 3M) may, forexample, be mentioned.

As a fluorinated alkylamine, perfluorotripropylamine orperfluorotributylamine may, for example, be mentioned. As afluoroalcohol, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol orhexafluoroisopropanol may, for example, be mentioned.

The non-fluorinated organic solvent may be a compound composed solely ofhydrogen atoms and carbon atoms or a compound composed solely ofhydrogen atoms, carbon atoms and oxygen atoms, preferred is ahydrocarbon type organic solvent, an alcohol type organic solvent, aketone type organic solvent, an ether type organic solvent, or an estertype organic solvent, and in view of solubility of the present compound,particularly preferred is a ketone type organic solvent.

The hydrocarbon type organic solvent is preferably hexane, heptane,cyclohexane or the like.

The alcohol type organic solvent is preferably methanol, ethanol,1-propanol, 2-propanol or the like.

The ketone type organic solvent is preferably acetone, methyl ethylketone, methyl isobutyl ketone or the like.

The ether type organic solvent is preferably diethyl ether,tetrahydrofuran, tetraethylene glycol dimethyl ether or the like.

The ester type organic solvent is preferably ethyl acetate, butylacetate or the like.

The liquid medium is preferably at least one organic solvent selectedfrom the group consisting of a fluorinated alkane, a fluorinatedaromatic compound, a fluoroalkyl ether, a compound composed solely ofhydrogen atoms and carbon atoms and a compound composed solely ofhydrogen atoms, carbon atoms and oxygen atoms.

Particularly preferred is at least one fluorinated organic solventselected from the group consisting of a fluorinated alkane, afluorinated aromatic compound and a fluoroalkyl ether.

With a view to improving the solubility of the present compound, theamount of such a solvent is at least 90 mass % based on the entireliquid medium.

[Substrate]

As a material for a substrate, an inorganic material, an organicmaterial or a composite material thereof may be mentioned.

As an inorganic material, glass, a single crystal material, metal, stoneor a composite material thereof may, for example, be mentioned, andpreferred is glass, a single crystal material or a composite materialthereof.

As glass, preferred is soda lime glass, alkali aluminosilicate glass,borosilicate glass, alkali-free glass, crystal glass or quartz glass,and particularly preferred is chemically tempered soda lime glass,chemically tempered alkali aluminosilicate glass or chemically temperedborosilicate glass.

As a single crystal material, preferred is zinc oxide, titanium oxide,diamond, sapphire or the like, and particularly preferred is sapphire.Sapphire is an α-type alumina (hexagonal) single crystal material havinga corundum structure. The crystal orientation surface of sapphire may beany of the following.

surface c (0, 0, 0, 1), surface a (1, 1, 2, 0),

surface m (1, 1, 0, 0), surface r (1, 1, 0, 2).

The crystal orientation surface of sapphire is preferably surface a inview of high strength. Further, in order to impart a desired hardnessand light transmitting property to the sapphire substrate itself,amorphous alumina, transparent alumina, another sapphire-like material,a polycrystal compound or the like may be combined. As a process forproducing sapphire may be a Verneuil method, a Czochralski method or EPG(Edge-defined film-fed Growth) method may be mentioned.

The organic material may, for example, be a resin. The resin ispreferably an acrylic resin or a polycarbonate resin.

The material for the substrate is preferably sapphire. When thesubstrate is a sapphire substrate, the present surface treatment agentcan impart more excellent water/oil repellency, fingerprint stainremovability, abrasion resistance and lubricity to the sapphiresubstrate surface. Therefore, the present surface treatment agent ispreferably a surface treatment agent for a sapphire substrate.

The substrate is preferably a substrate having a light transmittingproperty (hereinafter referred to also as a transparent substrate). “Alight transmitting property” means that the normal incidence visibletransmittance in accordance with JIS R1306 is at least 25%, preferablyat least 50%.

(Surface Layer)

The thickness of the surface layer is preferably from 1 to 100 nm,particularly preferably from 1 to 50 nm. When the thickness of thesurface layer is at least the lower limit value of the above range, thewater/oil repellency and the fingerprint strain removability areexcellent. When it is at most the upper limit value of the above range,the cost can be reduced, and further the light transmittance of asapphire substrate having such a surface layer becomes high.

Further, the thickness of the surface layer can be obtained in such amanner that an X-ray diffractometer ATX-G (manufactured by RigakuCorporation) for thin-film analysis is used to obtain an interferencepattern of reflected X-rays by means of an X-ray reflectance method, anda film thickness is calculated from the oscillation period of theinterference pattern.

(Production Process)

A process for producing a substrate having a surface layer has a step oftreating the substrate surface by using the present surface treatmentagent or coating liquid of the present invention. The treating methodmay be a dry coating method or an wet coating method.

<Dry Coating Method>

A process for producing a substrate having a surface layer by means of adry coating method, has a step of dry coating the substrate surface withthe surface treatment agent of the present invention.

The dry coating method may, for example, be a technique such as vacuumdeposition, CVD or sputtering. With a view to suppressing decompositionof the present compound and in view of simplicity of an apparatus, avacuum deposition method is preferred. The vacuum deposition method canbe classified into a resistance heating method, an electron beam heatingmethod, a high frequency induction heating method, a reactive depositionmethod, a molecular beam epitaxy method, a hot wall deposition method,an ion plating method, a cluster ion beam method, etc., and any methodcan be used. A resistance heating method can be suitably used with aview to suppressing decomposition of the present compound and in view ofsimplicity of an apparatus. A vacuum deposition apparatus is notparticularly limited, and a known apparatus may be used.

In a case where a vacuum deposition method is employed, the filmdeposition conditions vary depending upon the type of the vacuumdeposition method to be applied, and in the case of a resistance heatingmethod, the degree of vacuum before deposition is preferably at most1×10⁻² Pa, particularly preferably at most 1×10⁻³ Pa. The heatingtemperature of the deposition source is preferably from 30 to 400° C.,particularly preferably from 50 to 300° C. When the heating temperatureis at least the lower limit value of the above range, the filmdeposition rate will be excellent. When it is at most the upper limitvalue of the above range, it is possible to impart water/oil repellency,abrasion resistance and fingerprint stain removability to the substratesurface without causing decomposition of the present compound. At thetime of vacuum deposition, the substrate temperature is preferablywithin a range of from room temperature (20 to 25° C.) to 200° C. Whenthe substrate temperature is at most 200° C., the film deposition ratewill be excellent. The upper limit value of the substrate temperature ismore preferably at most 150° C., particularly preferably at most 100° C.

<Wet Coating Method>

A process for producing a substrate having a surface layer by means of awet coating method, has a step of coating the substrate surface with thesurface treatment agent or coating liquid of the present invention. Inthe case of using a coating liquid, a step of removing a liquid mediumis further included.

The coating method is preferably a spin coating method, a wipe coatingmethod, a spray coating method, a squeegee coating method, a dip coatingmethod, a die coating method, an ink jet method, a flow coating method,a roll coating method, a casting method, a Langmuir-Blodgett method or agravure coating method.

The method for removing a liquid medium may be heating, vacuuming, andheating and vacuuming. The temperature for drying is preferably from 10to 300° C., particularly preferably from 20 to 200° C.

<Post Treatment>

After the surface layer is formed on the substrate, an operation topromote the reaction of the present compound with the substrate may becarried out, as the case requires, in order to improve the abrasionresistance on the substrate surface. Such an operation may, for example,be e.g. heating or moisturizing. For example, a substrate having thesurface layer formed thereon may be heated in an atmosphere containingmoisture, whereby it is possible to promote the reaction such as areaction of e.g. a hydroxy group present on the substrate surface with ahydroxy group in the phosphoric acid group. After the surface treatment,a compound in the surface-treated layer which is not chemically bondedto another compound or the substrate, may be removed as the caserequires. As a specific method, for example, a method of washing thesurface-treated layer with a solvent, or a method of wiping thesurface-treated layer with cloth impregnated with a solvent, may bementioned.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples. In thefollowing, “%” means “mass %” unless otherwise specified. Ex. 1 to 7 areExamples of the present invention, and Ex. 8 is Comparative Example.

[Evaluation Methods]

(Method for Measuring Water Contact Angle and n-Hexadecane ContactAngle)

The contact angle of about 2 μL of distilled water or n-hexadecaneplaced on the surface of a surface layer of a substrate was measured bya contact angle measuring apparatus DM-500 (manufactured by KyowaInterface Science Co., Ltd.).

Measurement was carried out on different five positions on the surfaceof a surface layer of a substrate, and their average value wascalculated. To calculate the contact angle, 2θ method was employed.

(Abrasion Resistance)

With respect to the substrate having a surface layer, in accordance withJIS L0849, a cellulose nonwoven fabric (product name: BEMCOT M-3,manufactured by Asahi Kasei Corporation) was reciprocated 1,000 timesunder a load of 1 kg by means of a reciprocal traverse tester(manufactured by KNT), whereupon the water contact angle and then-hexadecane contact angle were measured.

The smaller the decrease of the water repellency (water contact angle)and the oil repellency (n-hexadecane contact angle) become when thenumber of abrasion times was increased, the smaller the decrease in theperformance by abrasion becomes, and the better the abrasion resistancebecomes.

(Fingerprint Stain Removability)

An artificial fingerprint liquid (a liquid composed of oleic acid andsqualene) was deposited on a flat surface of a silicon rubber stopper,and then, excess oil was wiped off with a nonwoven fabric (BEMCOT M-3,manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp.On a surface layer of a substrate having the surface layer, thefingerprint stamp was placed and pressed under a load of 1 kg for 10seconds so that the fingerprint was attached on the entire surface ofthe surface layer of the substrate. Then, the fingerprint attached onthe surface layer was wiped off under a load of 500 g by means of areciprocal traverse tester (manufactured by KNT) having tissue paperattached. The haze value was measured after every wiping reciprocation,and if it reached 0.5 or lower within 10 wiping reciprocations, such acase was taken as “acceptable”, and if it failed to reach 0.5 or lower,such a case was taken as “not acceptable”.

<Dynamic Friction Coefficient>

By means of a variable normal load friction and wear measurement systemHHS2000 (manufactured by SHINTO Scientific Co., Ltd.), the dynamicfriction coefficient of a substrate having a surface layer against anartificial skin (PBZ13001, manufactured by Idemitsu Technofine) wasmeasured under conditions of a contact area of 3 cm×3 cm and a load of100 g.

The smaller the dynamic friction coefficient, the better the lubricity.

Ex. 1: Production of Compound (1a-1-1) Ex. 1-1

Into a 300 mL three-necked round-bottomed flask, 14.1 g of a sodiumborohydride powder was put, and 350 g of ASAHIKLIN (tradename) AK-225(product name of a mixture of 48 mol % of HCFC-225ca and 52 mol % ofHCFC-225cb, manufactured by Asahi Glass Company, Limited, hereinafter,referred to also as “AK-225”) was added. While cooling and stirring inan ice bath, a solution having 100 g of compound (12a), 15.8 g ofmethanol and 22 g of AK-225 mixed, was slowly dropwise added from adropping funnel in a nitrogen atmosphere so that the internaltemperature would not exceed 10° C. After dropwise addition of theentire amount, a solution having 10 g of methanol and 10 g of AK-225mixed, was dropwise added. Then, the ice bath was removed, and whileraising the temperature slowly to room temperature, stirring wascontinued. After stirring at room temperature for 12 hours, the reactionmixture was cooled again in an ice bath, and an aqueous hydrochloricacid solution was dropwise added until the liquid became acidic. Aftertermination of the reaction, the reaction mixture was washed once withwater and once with a saturated aqueous sodium chloride solution,whereupon an organic phase was recovered. The recovered organic phasewas dried over magnesium sulfate, and then, the solid content wasfiltered off, and the filtrate was concentrated by an evaporator. Therecovered concentrated liquid was distilled under reduced pressure toobtain 80.6 g (yield: 88%) of compound (11a).

CF₂═CFO—CF₂CF₂CF₂C(═O)OCH₃  (12a)

CF₂═CFO—CF₂CF₂CF₂CH₂OH  (11a)

NMR Spectrum of Compound (11a):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 2.2 (1H), 4.1 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −85.6 (2F), −114.0 (1F), −122.2 (1F), −123.3 (2F), −127.4 (2F),−135.2 (1F).

Ex. 1-2

Into a 50 mL eggplant flask connected to a reflux condenser, 5.01 g ofcompound (11a) obtained in Ex. 1-1 and 5.06 g of methanol were put, and0.54 g of potassium hydroxide pellets were added. After stirring at 25°C. all-night in a nitrogen atmosphere, excess potassium hydroxide wastreated by adding an aqueous hydrochloric acid solution, and water andAK-225 were added to carry out liquid separation treatment. Afterwashing with water three times, the organic phase was recovered andconcentrated by an evaporator to obtain 5.14 g of a methanol adduct.Into a 50 mL eggplant flask connected to a reflux condenser, 1.0 g ofthe methanol adduct and 0.13 g of potassium hydroxide pellets were addedagain, and 10.86 g of compound (11a) was dropwise added while heating to100° C. Stirring was further carried out for 9 hours while maintaining100° C., excess potassium hydroxide was treated by adding an aqueoushydrochloric acid solution, and water and AK-225 were added to carry outliquid separation treatment. After washing three times with water, theorganic phase was recovered and concentrated by an evaporator to obtain11 g of an oligomer with a high viscosity. It was diluted again withAK-225 to two times, and developed and fractionated by silica gel columnchromatography (developing solvent: AK-225). With respect to eachfraction, an average value of unit number (n+1) was obtained from theintegrated value of ¹⁹F-NMR. 4.76 g of compound (10a-1) having fractionswith an average value of (n6+1) being from 7 to 10 in the followingformula (10a-1) put together, was obtained.

CH₃—O—(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(n6+1)—H  (10a-1)

NMR Spectrum of Compound (10a-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 3.7 (3H), 4.0 (2H), 4.4 (18.4H), 6.0 to 6.2 (9.2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −84.7 to −87.0 (18.4F), −89.4 to −91.6 (18.4F), −121.5 (16.4F),−123.4 (2F), −128.0 (18.4F), −145.3 (9.2F).

Average value of unit number (n6+1): 9.2

Ex. 1-3

Into a 200 mL eggplant flask connected to a reflux condenser, 100 g ofcompound (10a-1) obtained in Ex. 1-2 was put, and 28.6 g of acetylchloride was dropwise added thereto over 20 minutes with stirring atroom temperature in a nitrogen atmosphere. Stirring was carried out at50° C. for 4.5 hours, whereupon disappearance of raw materials wasconfirmed by means of ¹H-NMR. The reaction solution was concentrated byan evaporator. The solution after the concentration was diluted withAK-225 and treated with 20 g of silica gel, and then a solid content wasremoved by filtration. The solution was concentrated again by anevaporator to obtain 98.1 g (yield: 97%) of compound (9a-1) having anaverage value of unit number (n6+1) being 9.2, in the following formula(9a-1).

CH₃—O—(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(n6+1)—C(═O)CH₃  (9a-1)

NMR Spectrum of Compound (9a-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform+R-113 (CCl₂FCClF₂),standard: TMS) δ (ppm): 2.0 (3H), 3.6 (3H), 4.4 to 4.9 (18.4H), 6.0 to6.2 (9.2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform+R-113, standard:CFC₃) δ (ppm): −85.5 to −86.7 (18.4F), −91.5 to −93.9 (18.4F), −121.7 to−122.8 (18.4F), −128.4 to −129.6 (18.4F), −145.9 (9.2F).

Average value of unit number (n6+1): 9.2

Ex. 1-4

An autoclave (made of nickel, internal capacity: 1 L) was provided, andat a gas discharge outlet of the autoclave, a condenser held at 25° C.,a NaF pellets-packed layer and a condenser held at 0° C. were set inseries. Further, a liquid-returning line to return a liquid condensedfrom the condenser held at 0° C. to the autoclave, was set.

Into the autoclave, 750 g of R-419 (CF₂ClCFClCF₂OCF₂CF₂Cl) was put andstirred while maintaining the temperature at 25° C. After blowingnitrogen gas at 25° C. for one hour into the autoclave, fluorine gasdiluted to 20 vol % with nitrogen gas (hereinafter referred to as the20% fluorine gas), was blown at 25° C. for one hour at a flow rate of5.3 L/hr. Then, while blowing the 20% fluorine gas at the same flowrate, a solution having 70 g of compound (9a-1) obtained in Ex. 1-3dissolved in 136 g of R-419, was injected into the autoclave over aperiod of 7.4 hours.

Then, while blowing the 20% fluorine gas at the same flow rate, theinternal pressure of the autoclave was raised to 0.15 MPa (gaugepressure). Into the autoclave, 4 mL of a benzene solution containing0.0056 g/mL of benzene in R-419, was injected while heating from 25° C.to 40° C., whereupon the benzene solution injection inlet of theautoclave was closed. After stirring for 20 minutes, 4 mL of the benzenesolution was injected again while maintaining the temperature at 40° C.,whereupon the injection inlet was closed. The same operation was furtherrepeated 4 times. The total injected amount of benzene was 0.1 g.

Further, stirring was continued for one hour while blowing the 20%fluorine gas at the same flow rate. Then, the internal pressure of theautoclave was adjusted to the atmospheric pressure, and nitrogen gas wasinjected for one hour. The content in the autoclave was concentrated byan evaporator to obtain 82.3 g (yield: 97%) of compound (7a-1) having anaverage value of unit number (n6) being 8.2 in the following formula(7a-1).

CF₃—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂—C(═O)OCH₃  (7a-1)

NMR Spectrum of Compound (7a-1):

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform+R-113, standard:CFC₃) δ (ppm): −57.3 (3F), −77.5 (3F), −85.0 (34.8F), −88.5 (2F), −90.5(34.8F), −92.5 (2F), −127.5 (36.8).

Average value of unit number (n6): 8.2

Ex. 1-5

Into a 500 mL round-bottomed eggplant flask made of atetrafluoroethylene-perfluoro(alkoxyvinyl ether) copolymer (PFA), 82.3 gof compound (7a-1) obtained in Ex. 1-4 and 250 mL of AK-225 were put.3.9 g of methanol was slowly dropwise added from a dropping funnel, in anitrogen atmosphere, followed by stirring for 12 hours. The reactionmixture was concentrated by an evaporator to obtain 77.7 g (yield: 100%)of compound (6a-1) having an average value of unit number (n6) being 8.2in the following formula (6a-1).

CF₃—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂—C(═O)OCH₃  (6a-1)

NMR Spectrum of Compound (6a-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform+R-113, standard: TMS)δ (ppm): 3.8 (3H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform+R-113, standard:CFCl₃) δ (ppm): −57.3 (3F), −84.9 (34.8F), −90.5 (34.8F), −92.5 (2F),−120.2 (2F), −127.3 (32.8F), 128.2 (2F).

Average value of unit number (n6): 8.2

Ex. 1-6

Into a 100 mL round-bottomed eggplant flask, 33.5 g of compound (6a-1)obtained in Ex. 1-5 and 0.59 g of H₂NCH₂CH₂OH were put, followed bystirring at room temperature for 9 hours. The resulting reaction productwas concentrated by an evaporator to obtain 33.8 g (yield: 100%) ofcompound (5a-1) having an average value of unit number (n6) being 8.2 inthe following formula (5a-1).

CF₃—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂—C(═O)HN—CH₂CH₂OH  (5a-1)

NMR Spectrum of Compound (5a-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform+R-113, standard: TMS)δ (ppm): 2.7 (2H), 3.5 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform+R-113, standard:CFCl₃) δ (ppm): −57.3 (3F), −84.9 (34.8F), −90.5 (34.8F), −92.5 (2F),−120.2 (2F), −127.3 (32.8F), 128.2 (2F).

Average value of unit number (n6): 8.2

Ex. 1-7

Into a 100 mL round-bottomed eggplant flask, 33.8 g of compound (5a-1)obtained in Ex. 1-6 and 1.51 g of phosphorus oxychloride were put,followed by stirring at room temperature for 9 hours. 2.0 g of water wasadded to the resulting solution, followed by stirring at roomtemperature for 30 minutes. The resulting reaction product wasconcentrated by an evaporator to obtain 34.6 g (yield: 100%) of compound(1a-1-1) having an average value of unit number (n6) being 8.2 in thefollowing formula (1a-1). The number average molecular weight ofcompound (1a-1-1) is 3,600.

CF₃—O—[(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(n6)—CF₂CF₂O]—CF₂CF₂CF₂—C(═O)HN—CH₂CH₂—O—P(═O)(OH)₂  (1a-1)

NMR Spectrum of Compound (1a-1-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform+R-113, standard: TMS)δ (ppm): 2.8 (2H), 3.4 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform+R-113, standard:CFCl₃) δ (ppm): −57.3 (3F), −84.9 (34.8F), −90.5 (34.8F), −92.5 (2F),−120.2 (2F), −127.3 (32.8F), 128.2 (2F)

Average value of unit number (n6): 8.2

Ex. 2: Production of Compound (1a-2-1) Ex. 2-1

Into a 500 mL three-necked round-bottomed flask, 1.04 g of potassiumhydroxide was put, and 83 g of tert-butanol and 125 g of1,3-dis(trifluoromethyl)benzene were added. The potassium hydroxide wasdissolved by stirring at room temperature, and 250 g of compound (4a-2)(FLUOROLINK D10/H: product name, manufactured by Solvay Solexis K.K.)was added thereto, followed by stirring for one hour. At roomtemperature, 38.2 g of perfluoro(propyl vinyl ether)(CF₃CF₂CF₂—O—CF═CF₂) was added, followed by stirring for further 24hours. Hydrochloric acid was added for neutralization, and water wasfurther added for liquid separation treatment. After washing three timeswith water, the organic phase was recovered and concentrated by anevaporator to obtain 288.0 g of a reaction crude liquid. It was againdiluted with 144 g of AC-2000 and developed and fractionated by silicagel column chromatography (developing solvent: AC-2000 and AE-3000),whereby 136.2 g (yield: 47%) of compound (3a-2) was obtained.

CF₃CF₂CF₂—O—CHFCF₂—O—CH₂—CF₂O[(CF₂)_(n7-1)(CF₂CF₂O)_(n8)]CF₂CH₂OH  (3a-2)

NMR Spectrum of Compound (3a-2):

¹H-NMR (300.4 MHz, solvent: deuterated acetone+R-113, standard: TMS) δ(ppm): 3.9 (2H), 4.6 (2H), 5.1 (1H), 6.3 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone+R-113, standard: CFCl₃)δ (ppm): −52.3 to −54.2 (11.2F), −77.7 to −88.2 (9F), −89.4 to −91.1(38.4F), −130.5 (2F), −145.2 (1F).

Average value of unit number (n7): 6.6

Average value of unit number (n8): 9.6

Ex. 2-2

Into a 50 mL two-necked round-bottomed flask, 391 mg of cesiumcarbonate, 1.50 g of compound (3a-2) and 106 mg of ethylene carbonatewere added, and heated and stirred at 160° C. for 36 hours. To theobtained solution, 15 g of AK-225 and 10 g of dilute hydrochloric acidwere added. The organic layer and the aqueous layer were separated, andthe organic layer was washed three times with 30 mL of ion-exchangedwater and dehydrated with sodium sulfate, followed by distilling off thesolvent under reduced pressure to obtain 1.07 g (yield: 70%) of compound(2a-2).

CF₃CF₂CF₂—O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n7-1)(CF₂CF₂O)_(n8)]CF₂CH₂O—CH₂CH₂OH  (2a-2)

NMR Spectrum of Compound (2a-2):

¹H-NMR (300.4 MHz, solvent: deuterated acetone+R-113, standard: TMS) δ(ppm): 3.69 (4H), 4.04 (2H), 4.64 (2H), 6.40 to 6.83 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone+R-113, standard: CFCl₃)δ (ppm): −52.3 to −54.2 (11.2F), −77.7 to −88.2 (9F), −89.4 to −91.1(38.4F), −130.5 (2F), −145.2 (1F).

Average value of unit number (n7): 6.6

Average value of unit number (n8): 9.6

Ex. 2-3

Into a 50 mL round-bottomed eggplant flask, 1.0 g of compound (2a-2)obtained in Ex. 2-2 and 65.9 mg of phosphorus oxychloride were added,followed by stirring at room temperature for 9 hours. 2.0 g of water wasadded to the resulting solution, followed by stirring at roomtemperature for 30 minutes. The resulting reaction product wasconcentrated by an evaporator to obtain 1.0 g (yield: 100%) of compound(1a-2-1). The number average molecular weight of compound (1a-2-1) is2,400.

CF₃CF₂CF₂—O—CHFCF₂—O—CH₂—CF₂O[(CF₂O)_(n7-1)(CF₂CF₂O)_(n8)]CF₂CH₂—O—CH₂CH₂—O—P(═O)(OH)₂  (1a-2-1)

NMR Spectrum of Compound (1a-2-1):

¹H-NMR (300.4 MHz, solvent: deuterated acetone+R-113, standard: TMS) δ(ppm): 3.69 (2H), 4.04 (2H), 4.32 (2H), 4.64 (2H), 6.40 to 6.83 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone+R-113, standard: CFCl₃)δ (ppm): −52.3 to −54.2 (11.2F), −77.7 to −88.2 (9F), −89.4 to −91.1(38.4F), −130.5 (2F), −145.2 (1F).

Ex. 3: Production of Compound (1a-3) Ex. 3-1

In accordance with a method described in Ex. 1 of JP-A-2011-116947, amixture of compounds (3a-3), (3a-3-2) and (4a-3) was obtained.

CF₃—O—[(CF₂O)_(n7)-1(CF₂CF₂O)_(n8)]CF₃  (3a-3-2)

CF₃—O—[(CF₂O)_(n7)-1(CF₂CF₂O)_(n8)]CF₂CH₂OH  (3a-3)

HOCH₂CF₂O[(CF₂)_(n7)-1(CF₂CF₂O)_(n8)]CF₂CH₂OH  (4a-3)

Average value of unit number (n7): 24

Average value of unit number (n8): 21

Ex. 3-2

200 g of the mixture obtained in Ex. (3-1) was diluted with 200 g ofAC-2000, and developed and fractionated by silica gel columnchromatography (developing solvent: AC-2000 and AE-3000), whereby 90 g(yield: 45%) of compound (3a-3) was obtained.

NMR Spectrum of Compound (3a-3):

¹H-NMR (300.4 MHz, solvent: deuterated acetone+R-113, standard: TMS) δ(ppm): 3.9 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone+R-113, standard: CFCl₃)δ (ppm): −52.3 to −54.2 (46F), −54.3 to −56.2 (3F) −78.8 to −81.8 (2F),−89.4 to −91.1 (84F)

Ex. 3-3

Into a 50 mL two-necked round-bottomed flask, 1.0 g of cesium carbonate,10 g of compound (3a-3) and 162 mg of ethylene carbonate were added, andheated and stirred at 160° C. for 36 hours. To the obtained solution, 50g of AK-225 and 10 g of dilute hydrochloric acid were added. The organiclayer and the aqueous layer were separated, and the organic layer waswashed three times with 30 mL of ion-exchanged water and dehydrated withsodium sulfate, followed by distilling off the solvent under reducedpressure to obtain 6.58 g (yield: 65%) of compound (2a-3).

CF₃—O—[(CF₂O)_(n7-1)(CF₂CF₂O)_(n8)]CF₂CH₂—O—CH₂CH₂OH  (2a-3)

Average value of unit number (n7): 24

Average value of unit number (n8): 21

NMR Spectrum of Compound (2a-3):

¹H-NMR (300.4 MHz, solvent: deuterated acetone+R-113, standard: TMS) δ(ppm): 3.69 (2H), 4.04 (2H), 4.64 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone+R-113, standard: CFCl₃)δ (ppm): −52.3 to −54.2 (46F), −54.3 to −56.2 (3F) −78.8 to −81.8 (2F),−89.4 to −91.1 (84F).

Ex. 3-4

Into a 50 mL round-bottomed flask, 1.0 g of compound (2a-3) obtained inEx. 3-3 and 30 mg of phosphorus oxychloride were added, and stirred atroom temperature for 9 hours. To the obtained solution, 2.0 g of waterwas added, followed by stirring at room temperature for 30 minutes. Theresulting reaction product was concentrated by an evaporator to obtain1.0 g (yield: 100%) of compound (1a-3). The number average molecularweight of compound (1a-3) was 5,600.

CF₃—O—[(CF₂O)_(n7-1)(CF₂CF₂O)_(n8)]CF₂CH₂—O—CH₂CH₂—O—P(═O)(OH)₂  (1a-3)

Average value of unit number (n7): 24

Average value of unit number (n8): 21

NMR Spectrum of Compound (1a-3):

¹H-NMR (300.4 MHz, solvent: deuterated acetone+R-113, standard: TMS) δ(ppm): 3.69 (2H), 3.84 (2H), 4.64 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone+R-113, standard: CFCl₃)δ (ppm): −52.3 to −54.2 (46F), −54.3 to −56.2 (3F) −78.8 to −81.8 (2F),−89.4 to −91.1 (84F).

Ex. 4 to 8: Production and Evaluation of Substrate Having Surface LayerEx. 4 to 7 <Preparation of Coating Liquid and Wet Coating Method>

The compound obtained in each of Ex. 1 to 3 and C₄F₉OC₂H₅(Novec-7200,product name, manufactured by 3M) as a liquid medium were mixed toprepare a coating liquid having a solid content concentration of 0.05%.A substrate was dipped in the coating liquid (dip coating method), leftto stand for 30 minutes and then pulled out. The substrate was dried at200° C. for 30 minutes and washed with AK-225 which is a fluorinatedsolvent, to obtain a substrate having a surface layer. The thickness ofthe surface layer was 10 nm. As the substrate, artificial sapphire(crystal orientation surface: surface c, manufactured by Shinkosha, Co.,Ltd.) or chemically tempered glass (alkali aminosilicate glass,manufactured by Asahi Glass Company, Limited) was used.

The evaluation results of water contact angle, n-hexadecane contactangle, abrasion resistance, fingerprint stain removability and dynamicfriction coefficient of the surface layer are shown in Table 1.

Ex. 8 <Preparation of Coating Liquid and Wet Coating Method>

Compound (1a-4) represented by the following formula (1a-4) described inNon-Patent Document J. Phys. Chem. C, 2007, 111, 3956-3962, andC₄F₉OC₂H₅(Novec-7200, product name, manufactured by 3M) as a liquidmedium, were mixed to prepare a coating liquid having a solid contentconcentration of 0.05%. A substrate was dipped in the coating liquid(dip coating method), left to stand for 30 minutes and then pulled out.The substrate was dried at 200° C. for 30 minutes and washed with AK-225to obtain a substrate having a surface layer. The thickness of thesurface layer was 10 nm. As the substrate, artificial sapphire (crystalorientation surface: surface c, manufactured by Shinkosha, Co., Ltd.)was used.

The evaluation results of water contact angel, n-hexadecane contactangle, abrasion resistance, fingerprint stain removability and dynamicfriction coefficient of the surface layer are shown in Table 1.

CF₃(CF₂)₇CH₂CH₂P(═O)(OH)₂  (1a-4)

TABLE 1 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Compound (1a-1-1) (1a-2-1) (1a-3)(1a-3) (1a-4) Substrate Artificial Artificial Artificial GlassArtificial sapphire sapphire sapphire sapphire Water contact angleInitial 115 113 113 111 108 (°) After 1,000 times of abrasion 114 112112 110 97 n-Hexadecane Initial 65 64 64 64 50 contact angle (°) After1,000 times of abrasion 64 64 63 60 37 Fingerprint stain removabilityAcceptable Acceptable Acceptable Acceptable Not Acceptable Dynamicfriction coefficient 0.40 0.32 0.35 0.35 0.60

From the results in Table 1, water/oil repellency, fingerprint stainremovability and lubricity were excellent in Ex. 4 to 7 wherein thepresent compound was used.

Further, in Ex. 4 to 7, the deterioration of water/oil repellency wassmall or hardly observed, and abrasion resistance was excellent, evenwhen abrasion was repeated 1,000 times to the substrate having thesurface layer. On the other hand, water/oil repellency, fingerprintstain removability and lubricity were poor in Ex. 8 wherein compound(1a-4) having no perfluoropolyether group was used. Further, in Ex. 8,water/oil repellency was significantly deteriorated, and abrasionresistance was poor when abrasion was repeated 1,000 times to thesubstrate having the surface layer.

Further, according to comparison of Ex. 4 to 6, in Ex. 4 whereincompound (1a-1-1) was used, water/oil repellency and abrasion resistancewere more improved as compared with Ex. 6 wherein compound (1a-3) wasused, and further, in Ex. 5 wherein compound (1a-2-1) was used, abrasionresistance and lubricity were more improved as compared with Ex. 6wherein compound (1a-3) was used.

INDUSTRIAL APPLICABILITY

A substrate having a surface layer formed by using the present surfacetreatment agent can be used for electronic materials or opticalmaterials (such as an endoscope lens, a mobile communication device, afingerprint reader, an automatic remitting machine, a goggle, a camera,an infrared imaging system, a lens, a touch panel or a window), orbuilding materials (such as a flooring material or a wall material).When the substrate is a transparent substrate, the substrate having asurface layer is preferably used for electronic materials or opticalmaterials, particularly preferably used for a member to constitute atouch panel. The touch panel is an input device of an input/displayapparatus (touch panel apparatus) having a display device combined withthe input device for inputting a contact position information upontouching with e.g. a finger. The touch panel is constituted by atransparent substrate and, depending upon the input detection system, atransparent conductive film, electrodes, a wiring, IC, etc. By using thesurface having a surface layer of a transparent substrate as the inputsurface of a touch panel, it is possible to obtain a touch panel havingexcellent finger print stain removability and lubricity. When thelubricity is excellent, the touch feeling of the touch panel will beexcellent, and the operation efficiency will be improve.

This application is a continuation of PCT Application No.PCT/JP2015/075736, filed on Sep. 10, 2015, which is based upon andclaims the benefit of priority from Japanese Patent Application No.2014-188789 filed on Sep. 17, 2014. The contents of those applicationsare incorporated herein by reference in their entireties.

1: A surface treatment agent, comprising a perfluoropolyethergroup-containing phosphate compound, wherein the perfluoropolyethergroup-containing phosphate compound is a compound represented by formula(1):B¹—(C_(m)F_(2m)O)_(n1)-A¹  (1) wherein A¹ is a monovalent organic grouphaving at least one phosphoric acid group at its terminal, B¹ isR^(F1)—O— or D¹-Q¹-O—CH₂— and a compound represented by the formula (1)wherein A¹ is a monovalent organic group having at least one phosphoricacid group at its terminal, B¹ is A²-O—, wherein a content of thecompound represented by the formula (1) wherein B¹ is A²-O— is from 10to 60 parts by mass, per 100 parts by mass in total of the compoundrepresented by the formula (1) wherein B¹ is R^(F1)—O— or D¹-O¹—O—CH₂—,wherein R^(F1) is a C₁₋₆ perfluoroalkyl group, D¹ is CF₃— or CF₃—O—, O¹is a C₁₋₂₀ fluoroalkylene group comprising a hydrogen atom, a C₂₋₂₀fluoroalkylene group comprising a hydrogen atom and having an ethericoxygen atom between carbon-carbon atoms, a C₁₋₂₀ alkylene group, or aC₂₋₂₀ alkylene group having an etheric oxygen atom between carbon-carbonatoms, and A² is a monovalent organic group having at least onephosphoric acid group at its terminal, m is an integer of from 1 to 6,and n1 is an integer of from 1 to 200, provided that when n1 is at least2, (C_(m)F_(2m)O)_(n1) may be one composed of at least two types of(C_(m)F_(2m)O) different in m. 2: (canceled) 3: The surface treatmentagent according to claim 1, wherein (C_(m)F_(2m)O)_(n1) is a grouprepresented by formula (2-1):(C_(r)F_(2r)O)_(n2)(C_(s)F_(2s)O)_(n3)  (2-1) wherein r is an integer offrom 1 to 3, s is an integer of from 3 to 6, provided that r and s arenot both 3, n2 is an integer of at least 1, n3 is an integer of at least1, provided that n2+n3 is an integer of from 2 to 200, and a bondingorder of (C_(r)F_(2r)O) and (C_(s)F_(2s)O) is not limited. 4: Thesurface treatment agent according to claim 1, wherein(C_(m)F_(2m)O)_(n1) is a group represented by formula (2-2):(CF₂O)_(n7)(CF₂CF₂O)_(n8)  (2-2) wherein n7 is an integer of at least 1,n8 is an integer of at least 1, provided that n7+n8 is an integer offrom 2 to 200, and a bonding order of (CF₂O) and (CF₂CF₂O) is notlimited. 5: The surface treatment agent according to claim 1, wherein A¹is a group represented by formula (3):-Q^(F1)(CX₂)_(w1)-E¹-Y¹—O—P(═O)(OH)₂  (3) wherein Q^(F1) is a C₁₋₂₀perfluoroalkylene group, CX₂ is CH₂ or CHF, w1 is 0 or 1, E¹ is a singlebond, —C(═O)NH— (provided that Y¹ is bonded to N), —OC(═O)NH— (providedthat Y¹ is bonded to N), —O—, —C(═O)O— (provided that Y¹ is bonded toO), —OC(═O)O—, —NHC(═O)NH— or —NHC(═O)O— (provided that Y¹ is bonded toO), wherein Y¹ is an alkylene group, a poly(oxyalkylene)-alkylene group,a cycloalkylene group, an arylene group, or an alkylene group in whichat least one of hydrogen atoms is substituted by a hydroxy group,provided that E¹ is not —O—, —OC(═O)NH— or —OC(═O)O— when w1 is 0, andY¹ is not an alkylene group when w1 is 1, CX₂ is CH₂ and E¹ is a singlebond. 6: The surface treatment agent according to claim 1, wherein Q¹ isa group represented by formula (4-1), (4-2) or (4-3):-Q^(F2)-O—CHFCF₂—  (4-1)-Q^(F2)-CHFCF₂—  (4-2)-Q^(F2)-C_(z)H_(2z)—  (4-3) wherein Q^(F2) is a single bond, a C₁₋₁₅perfluoroalkylene group, or a C₂₋₁₅ perfluoroalkylene group having anetheric oxygen atom between carbon-carbon atoms, Q^(F2) is bonded to D¹,and z is an integer of from 1 to 4, provided that Q^(F2) is not a singlebond in the formula (4-1) and (4-2) when D¹ is CF₃—O—. 7: The surfacetreatment agent according to claim 1, wherein a number average molecularweight (Mn) of the compound represented by the formula (1) is 2,000 to10,000. 8: The surface treatment agent according to claim 1, wherein inthe compound represented by the formula (1), B¹ is R^(F1)—O— orD¹-Q¹-O—CH₂—. 9-10: (canceled) 11: The surface treatment agent accordingto claim 1, which is suitable for treating a surface of a sapphiresubstrate. 12: A coating agent comprising the surface treatment agent ofclaim 1 and a liquid medium. 13: A substrate having a surface layerformed from the surface treatment agent of claim
 1. 14: (canceled)